Fungi and bacteria resistant polyvinyl halide compositions



Patented Mar. 24, 1953 tune: out BAo T imA RESIST NT. Poir- VINYL HALIDE COMPOSITIONS Joseph R; Darby, Richmond Heights, Mo.,- as

sig'nor to Monsanto Chemical Company, St. Louis, Mo.-, a corporation of Delaware No Drawing. Application March 23, 1951, Serial No. 218,061

, p 14 Claims. 1

This invention relates to improved resinous compositions containing vinyl halide polymers. More particularly, this invention relates to plas-- ticized resinous compositions having improved resistance to deterioration due to attack by such micro-organisms as fungi and bacteria, and containing polyvinyl halide, copolymers containing combined vinyl halide, or combinations thereof containing combined vih yl halide, collectively and broadly referred to herein as polyvinyl halide compositions.

Polyvinyl halide compositions have found many useful applications because of their wide range of el-astomeric and mechanical properties coupled with their extreme resistance to oxida= tion, organic solvents, acids and alkalies. Typical of such applications are calendered andsheeting for wearing apparel, shower curtains and seat and cushion coverings. In such applications, polyvinyl halide compositions have found utility as a free or unsupported film but more frequently polyvinyl halide compositions have been used to coat such textiles as cotton, wool, silk, rayon, and nylon thereby obtaining a composition or fabric for use in the above mentioned applications which combines the desirable properties of the textile and the desirable properties of the polyvinyl halide composition. Such polyvinyl halide compositions frequently contain plasticizers or stabilizers which have I their origin in animal or vegetable sources, or the base material of coated compositions frequently contains materials which have their origin in animal or vegetable sources which thereby render the resultant composition quite susceptible to deteriorating attack by such micro-organisms as fuhgi and bacteria. Such deterioration of polyvinyl halide compositions or polyvinyl halide coated compositions seriously hinders full scale utility or the compositions particularly in those areas and those applications which are conducive to such an attack.

2 the copper 8 quiholliilate begins to crystallize or bloom on the surface of the composition indicating incompatibility and renderin the coin position unfit for use.

A more recent development in the field of fungi and bacteria resistant plasticized polyvinyl halide compositions has been the discovery of the use of the condensation product of toluenesulfonamide and formaldehyde as a comp-atibilizing agent for copper 8=quiiiolinolate in such compositions. According to this procedure, a compati'ble plasticized polyvinyl halide composition containing copper B-quin-olinolate is prepared by incorporating therein the condensation product of toluenesulfonamide and formaldehyde. While this procedure has been most successful in many applications, a surprising phenomenon has been found to exist. lit has been observed that if such a composition is utilized in an application which prevents the composition from being exposed to ultra-violet light, after a period of time copper 8-'quinolinolate begins to exude or crystallize upon the surface of the composition, thereby in dicating incompatibility. Thus, if such composi tiohs are utilized as the insulation or coating for wires which will be constantly kept under ground or sealed in the walls of buildings, or if such compositions are used as the inside coating for tent fabrics in which applications the compositions will never be subject to the effects of ultra-violet light, after a short eriod or time copper suinounoiate can observed (flyS'fiaHiZing upon the surface of such compositions.

It is an bbjeet of this invention, therefore, to

provide improved pl-asticiZed polyvinyl halide compositions having incorporated therein copper 8-quinolinolate so as to render them resistant to attack by fungi and bacteria, which compositions will remain compatible and homogeneous with no evidence of crystallization o blooming of the copper 8-ouii1o1ino1ate under any conditions or application or use. Further otj'ects win become apparent from the description of the novel process of this invention.

It has now been discovered that if a minor amount of a compound selected from the group consisting or cadmium iieir'ioleat and calcium ricinoleate is incorporated into a poit 'viny1 halide composition comprising vinyl halide-containing polymer, a pl-asticizer for said polymer, the condensation product of toluehesulfo'namid-e and formaldehyde and a minor amount of copper 8-.

quinoliholate, a fungi and bacteria resistant plas- 'ticiaed poly "Y1 halide compos tion results which Will remain" compatible even the absence of V 3 ultra-violet radiation. According to this invention, therefore, compatible fungi and bacteria resistant plasticized polyvinyl halide compositions are provided comprising a vinyl halide-containing polymer, a plasticizer for said polymer, the condensation product of toluenesulfon'amide and formaldehyde, a minor amount of copper 8- quinolinolate and a minor amount of a compound selected from the group consisting of calcium ricinoleate and cadmium ricinoleate.

The following examples are illustrative, but not limitative, of this invention. All parts are by weight unless otherwise noted.

Example a 100 parts of polyvinyl chloride, 2.5 parts of tricresyl phosphate, 2.5 parts of butyl -acetyl ricinoleate and 1 part of copper B-quinolinolate are mixed together at room temperature in a suitable container. The mixture is then placed on a differential speed roll mill and further mixed and fluxed for 5 minutes at 160 C. At the end of this time, a homogeneous composition is formed which is sheeted off the roll mill. 0.040 inch thick sheets of the composition so prepared are then molded at a temperature of 160 C. under a pressure of 2000 pounds per square inch. After removal from the mold, crystals of copper 8- quinolinolate can be observed on the surface of the composition thereby indicating incompatibility of the copper 8-quinolinolate- Example II The procedure set forth in Example I is repeated utilizing in addition to the ingredients set forth therein, 5 parts of the toluenesulfonamideformaldehyde condensation product. The molded specimen when removed from the mold is free of any signs of blooming or crystallization, thereby indicating a, compatible composition. In order to further test the compatibility of the composition so prepared, specimens molded as above described are allowed to stand on a table in ordinary daylight. Similar specimens are placed in a. closed cabinet from which all daylight is excluded. After about 30 days, the specimens which are exposed to daylight are free of any signs of blooming or crystallization, indicating a compatible composition, whereas the compositions which are kept in the cabinet from which daylight is excluded, exhibit crystallization or blooming of copper 8-quin0lin01ate on the surface of the composition, thereby indicating that the copper 8-quinolinolate has become incompatible with the resinous composition.

Example III I 100 parts of polyvinyl chloride, 2.5 parts of tricresyl phosphate, 2.5 parts of butyl acetyl ricinoleate, 1 part of copper S-quinolinolate, 5 parts of the toluenesulfonamide-formaldehyde condensation product and 2 parts of cadmium ricinoleate are processed in accordance with the procedure described in Example I. The molded specimens are free of any signs of blooming or crystallization, thereby indicating a compatible composition. Specimens of the molded composition thus prepared are allowed to stand in the presence of daylight while similar specimens are placed in a cabinet from which daylight is excluded. After 90 days the specimens which have been allowed to stand in the presence of daylight and those specimens which have been allowed to stand in the absence of daylight are free from any signs of blooming or crystallization, thereby in- 4 dicating completely compatibile compositions. It is evident, therefore, that the incorporation of a minor amount of cadmium ricinoleate into the plasticized composition permitted the preparation of a completely compatible plasticized polyvinyl halide composition which composition retained its compatibility even on prolonged standing in the absence of ultra-violet light.

Compositions as above described in Example III are prepared with the exception that the 5 parts of the toluenesulfonamide-formaldehyde condensation product are eliminated from the formulation. Molded specimens thus prepared which are allowed to stand in the absence of daylight soon exhibit incompatibility.

Example IV A composition comprising 100 parts of polyvinyl chloride, 25 parts of tricresyl phosphate, 25 parts of butyl acetyl ricinoleate, and 0.2 part of copper S-quinolinolate is processed in the manner described in Example I. The molded specimen exhibits blooming and a crystal formation on the surface thereby indicating that copper 8-quinolinolate is incompatible in this composition.

Example V The procedure set forth in Example IV is reppeated utilizing in addition to the ingredients set forth therein, 1 part of the condensation product of toluenesulfonamide and formaldehyde. The molded specimen when removed from the mold is free of any signs of blooming or crystallizatioir, thereby indicating a compatible composition. Specimens of the molded composition are allowed to stand on a table in ordinary daylight while similar specimens are placed in a closed cabinet from which all daylight is excluded. After about 30 days, the specimens which are exposed to daylight are free of any signs of blooming or crystallization whereas the specimens which are kept in the cabinet from which daylight is excluded exhibit crystallization or blooming of copper 8-quinolinol-ate on the surface of the composition.

Example VI The procedure set forth in Example IV is repeated utilizing the following ingredients:

100 parts polyvinyl chloride 25 parts tricresyl phosphate 25 parts butyl acetyl ricinoleate 0.2 parts copper 8-quinolinolate 1 part condensation product of toluenesulfonamide and formaldehyde 0.5 part calcium ricinoleate The molded specimens are free of any signs of blooming or crystallization even after having been allowed to stand for days in the absence of ultra-violet light.

Example VII The procedure set forth in Example IV is repeated utilizing the following ingredients:

parts polyvinyl chloride 25 parts tricresyl phosphate 25 parts butyl acetyl ricinoleate The molded specimens are free of any signs of blooming or crystallization even after having been allowed to standfo'r 90 days in the absence of ultra violet light. i I

A cotton duck fabric is coated with the composition described in Example VII by the calendering method which consists in simultaneously passing the fabric and the polyvinyl chloride composition through a conventional fourroll calender. The. coated cotton duck fabric in ad dition to possessing the desirable characteristics of thefabric and the polyvinyl chloride coating, is extremely resistant to attack by fungi and bacteria by. virtue of the composition having incorporated therein copper 8-quinolinolate.-

j Example VIII A composition comprising 100 parts of polyvinyl chloride, 50 parts of dioctyl phthalate and 3 parts of copper 8-quinolinolate is prepared in the manner described in Example I. The molded specimen exhibits blooming and crystallization on thesurface indicating the incompatibility of copper S-Quinolinolate in this composition.

Example IX The procedure set forth in Example VIII is repeated utilizing in addition to the ingredients set forth therein, 2 parts of the condensation product of toluenesulfonamide and formaldehyde. Molded specimens of the composition thus prepared are allowed to stand in the presence of daylight while similar specimens of the molded compositions are allowed to stand in the absence of daylight. Those compositions which are subjected to daylight or ultra-violet light after a period of time show no signs of incompatibility, while those compositions which are allowed to stand in the absence of daylight, after a period of time begin to show incompatibility.

Example X The procedure set forth in Example VIII is repeated utilizing the following ingredients:

100 parts polyvinyl chloride 50 parts dioctyl phthalate 2 parts condensation product of toluenesulfonamide and formaldehyde 3 parts copper 8-quinolinolate 2 parts cadmium ricinoleate Specimens of the molded composition are allowed to stand in the presence of daylight while similar specimens are allowed to stand in the absence of daylight. After prolonged standing under such conditions, neither specimen shows any sign of incompatibility.

Example XI The procedure set forth in Example X is repeated utilizing 100 parts of dioctyl phthalate in place. of the 50 parts of dioctyl phthalate. The molded specimens thus obtained are compatible and retain their compatibility even after prolonged standing in the absence of ultra-violet light. I

I Example XII The procedure set forth in Example X is re peated utilizing the following ingredients: 100 parts polyvinyl chloride 50 parts dioctyl phthalate 3 parts copper y8-quinolinolate 2 parts calcium ricinoleate The molded specimens exhibit blooming anda crystal formation on the surface thereby indi cating that copper 8-qui-nol-i'nolate is incompatiblej-irrthiscompositiom 6 mama-1e x111 I The resulting composition is completely compatibile even after prolonged standing in the absence of ultra-violet light.

Emmple XIV The procedure set forth in Example VIII is repeated utilizing the following ingredients:

100 parts polyvinyl chloride 7 50 parts dioctyl phthalat'e 2 parts condensation product of toiueiiesiiifonamide and formaldehyde 3 parts copper 8-quinolinolate 2 parts calcium ricinoleate Specimens of the molded composition are allowed to stand in the presence of daylight while similar specimens are allowed to stand in the absence of daylight. After prolonged standing under such conditions, neither specimen shows any sign of incompatibility.

Example Theprocedure set forth in Examples VIII, and): are repeated utilizing in place of the polyvinyl chloride a polymerized Vinyl resin containing parts of combined vinyl chloride and 10 parts of combined vinyl acetate. The properties of the compositions thusprepared are similar to those Obtained in Examples VIII, IX and X.

The procedures set forth in Examples VIII, and X are repeated utilizing in place of the polyvinyl chloride a polymerized Vinyl resin containing 90 arts of combined vinyl chloride and 10 parts of diethyl maleate. The properties of the compositions thus prepared are similar to those obtained in Examples VIII, and

Examples I, IV, and (in part) as hereinbefore set forth Very clearly indicate the extreme incompatibility of copper 8=quin olinolate in polyvinyl halide compositions when such compositions are prepared according to the methods heretofore practiced. Examples II, V, Di and XV (in part) illustrate the phenomenon of the compatibility of certain plasticized polyvinyl halide compositions containing copper 8- quinolinolate in the presence of ultra-violet light and the unusual incompatibility of such com positions in the absence of ultra-violet light when such compositions are prepared in accordance with recently developed processes. Examples III,

VI, VII, X, XI, XIII, IHV and XV (in part) are indicative of the oustanding compatibility of copper 8-quinolinolate in plasticized polyvinyl halide compositions obtained when prepared in accordance'with the process of this invention whereby compositions are obtained which remain fully Chaetomium globosttm,- Mctarrmzium 'spi,"

Organism Fungus Activity on the Sample Chaetomium globosum No growth of the organism on the sample. Metarrhizium sp Do. Aspergillus niger Do. Penicillium sp Do.

A further unsupported polyvinyl chloride film was prepared containing 100 parts of polyvinyl chloride, 25 parts of butyl acetyl ricinoleate and 25 parts of tricresyl phosphate. When this composition was inoculated with the above mentioned organisms, a severe growth of the organism took place on the sample, indicating the outstanding fungi and bacteria resistant characteristics of the novel compositions of this invention.

While various specific embodiments of this invention have been particularly illustrated in the preceding examples, it will be obvious to those skilled in the art that substantial variation from the conditions set forth in these examples is possible without departing from the scope of this invention. For example, in order to obtain fungi or bacteria resistant polyvinyl halide compositions, it is preferable that such compositions contain from about 0.1 to about 2.5 parts by weight of copper B-quinolinolate per 100 parts of polymerized vinyl halide resin. At times, under severe conditions, it is desirable to increase the copper 8-c1uinolinolate content to about parts by weight per 100 parts of resin or even to parts by weight per 100 parts of resin.

The compositions of this invention may contain any plasticizer for the polymerized vinyl halide resin utilized in the composition, and the quantity of the plasticizer utilized may be varied over a substantial range. Particularly advantageous compositions are those which contain from about 5 parts to about 150 parts by weight of the plasticizer per 100 parts of the polymerized vinyl halide 'resin. Typical of the various plasticizers which may be utilized in the compositions of this invention are the aryl alkane sulfonates; the various esters of phthalic acid such as dibutyl phthalate, dioctyl phthalate, dinonyl phthalate,

and alkyl benzyl phthalates; the various esters of orthophosphoric acid such as the alkyl diaryl phosphates, tricresyl phosphate, trioctyl phosphate, etc.; esters of aliphatic dicarboxylic acids such as dibutyl sebacate, dioctyl adipate, etc.; alkyl phthalyl alkyl glycolates such as butyl phthalyl butyl glycolate, etc.; and resinous plasticizers such as the condensation products of polycarboxylic acids and polyhydric alcohols.

In addition to the usual plasticizers for polyvinyl halide resins, the compositions of this invention may also have incorporated therein various pigments, fillers, stabilizers, both heat and light, etc.

The quantity of the toluenesulfonamide-formaldehyde condensation product utilized in the compositions of this invention may also be varied over a substantial range. Particularly advantageous compositions are those containing from about 1 to about 5 parts by weight of the toluenesulfonamide-formaldehyde condensation product per 100- parts of the polyvinyl halide resin utilized. At times it may be desirable to increase the toluene-sulfonamide-formaldehyde condensation product content to as high as about 25 parts by weight per 100 parts of resin.

It is preferred that the toluenesulfonamideformaldehyde condensation product be obtained by the condensation of' 1 mol of formaldehyde with approximately 1 mol of toluenesulfonamide. The molar ratio of toluenesulfonamide to formaldehyde may, however, be varied over a wide range without affecting the compatibilizing efiect of the resultant condensation product. Excessive quantities of formaldehyde do not materially alter the nature of the reaction product as these excessive quantities are lost during the reaction. Excessive quantities of toluenesulfonamide result in a condenesation product having a higher free amide content which does not materially affect the compatibilizing efiect of the condensation product on copper B-quinolinolate.

The quantity of calcium ricinoleate or cadmium ricinoleate utilized in the novel compositions of this invention may also be varied over a substantial range. Particularly advantageous compositions are those containing from about 0.1 to about 5 parts by weight of cadmium ricinoleate or calcium ricinoleate per 100 parts of the polyvinyl halide resin utilized.

As indicated by the examples, copolymers of a vinyl halide and other unsaturated materials 00- polymerizable therewith may be utilized in this invention. For example, copolymers of vinyl chloride with such materials as vinylidene chloride, vinyl esters of carboxylic acids, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; esters of unsaturated acids, for example, alkyl acrylates, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, allyl acrylate and the corresponding esters of methacrylic acid; vinyl aromatic compounds, for example, styrene, ortho-chloro-s'tyrene, parachlorostyrene, 2,5-dichlorostyrene, 2,4-dichlorostyrene, para-ethyl styrene, divinyl benzene, vinyl naphthanate, alpha-methyl styrene, dienes, such as butadiene, chloroprene; amides, such as acrylic acid amide, acrylic acid anilide; nitriles, such as acrylic acid nitrile; esters of alpha, beta-unsaturated carboxylic acids, for example, the methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, allyl, methallyl, and phenyl esters of m-aleic, crotonic, itaconic, fumaric acids and the like, may be utilized. The class of copolymers in which a predominant portion i. e., more than 50% by weight, of the copolymer is made from vinyl chloride, represents a preferred class of polymers to be utilized in this invention.

A particularly preferred embodiment of this invention comprises the use of a polymer prepared by copolymerizing vinyl chloride and an ester of an alpha, beta-unsaturated dicarboxylic acid, such as diethyl maleate, in which 5 to 20 parts by weight of diethyl maleate are utilized for every 95 to parts by weight of vinyl chloride. Among the preferred esters of alpha, beta-unsaturated dicarboxylic acids are the alkyl esters in which the allzyl group contains from 1 to 8 carbon atoms.

in addition to the above described vinyl chloride-containing polymers, similar polymers wherein the vinyl chloride is replaced, either in whole or in part, by other vinyl halides may be utilized. Typical of such other vinyl halides are vinyl bromide, vinyl fluoride, etc.

The compositions of this invention may be effectively utilized to produce free or unsupported polyvinyl halide films and sheeting which will be resistant to the deteriorating effects of fungi and bacteria. Ihese compatible compositions may ;also be applied as a coating to various textiles,

such as, roads. wool, rayon, silk, and nylon,- and ,terioration due to attack by fungi and bacteria.

The plasticizer, copper S-quinolinolate, cad mium ricinoleate or calcium ricinoleate and toluenesulfonamide-formaldehyde condensation product may be incorporated into the particular polym rized vinyl halide resin utilized accordin to any suitable method including those commonly used and well known to those skilled in the art of compounding vinyl halide resin compositions. Thus, these ingredients may be incorporated with the polyvinyl halide resin on a diiferential speed roll mill or in an internal mixer. These ingredients may also be added to a latex of the resin, to an emulsion of the vinyl halide monomer prior to polymerization to form the resin, or to a solution of the polymerized vinyl halide resin in a suitable solvent.

What is claimed is:

1. Fungi and bacteria resistant vinyl halidecontaining polymeric compositions comprising a vinyl halide-containing resin, a plasticizer for said resin, the condensation product of toluenesulfonamide and formaldehyde, a minor but effective amount of copper 8-quinolinolate and a compound selected from the group consisting of cadmium ricinoleate and calcium ricinoleate, the amount of the condensation product of toluenesulfonamide and formaldehyde being suflicient to compatibilize the copper -8-quinolinolate in the resin composition and the amount of ricinoleate being a minor amount suiiicient to prevent crystallization or blooming of the copper 8-quinolinolate from the resin composition under conditions of application and use.

, 2. Fungi and bacteria resistant vinyl halidecontaining polymeric compositions comprising a vinyl halide-containing resin, a plasticizer for said resin, from about 1 to about 25 parts by weight of the condensation product of toluenesulfonamide and formaldehyde per 100 parts of said resin, from about 0.1 to about 10 parts by weight of copper B-quinolinolate per 100 parts of said resin and from about 0.1 to about 5 parts by weight of a compound selected from the group consisting of cadmium ricinoleate and calcium ricinoleate per 100 parts of said resin.

3. Fungi and bacteria resistant vinyl halidecontaining polymeric compositions comprising a vinyl halide-containing resin copolymer in which more than 50% by weight is made from a vinyl halide, a plasticizer for said resin, from about 1 "to about 5 parts by weight of the condensation product of toluenesulfonamide and formaldehyde per 100 parts of said resin, from about 0.1 to about 5 parts by Weight of copper 8-quinolinol'ate per 100 parts of said resin and from about 0.1 to about 5 parts by weight of a compound selected from the group consisting of cadmium ricinoleate and calcium ricinoleate per 100 parts of said resin.

i. Fungi and bacteria resistant vinyl chloridecontaining polymeric compositions comprising a vinyl chloride-containing resin copolymer in which more than 50% by weight is made from fvinyl hrones; piasuciza rbr said resin, the condensation product oftoluenesulfonamide and formaldehyde, aminor but effective amount of copper 8-quinolinolate and acompound selected from the group consisting' of cadmium ricinoleate and calciumricinoleate, the amount of the condensation product of toluenesulfonamide and formaldehyde being-sufficient to compatibilize the copper 8-quinolinolate inthe resin composition and the amount-of ricinoleate being a minor amount suiiicient to prevent crystallization or blooming of the copperl8-quinolinolate from the resin composition under conditions of application and use. l I

5'. Fungi and bacteria resistant vinyl chloridecontaining polymeric compositions comprising a vinyl chloride-containing resin, a plasticizer for said resin, from about 1 to about 25 parts by weight of the condensation product of toluenesulfonamideiand formaldehyde :per parts of said resin, from about 0.1 to about 10 parts by weight of copper s-quinolinolate per 100 parts of said resin and from about 0.1 to about 5 parts by weight of a compound selected from the group consisting of cadmium ricinoleate and calcium ricinoleate per 100 parts of said resin.

6. Fungi and bacteria resistant vinyl chloridecontaining polymeric compositions comprising a vinyl chloride-containing resin, a plasticizer for said resin, from about 1 to about 5 parts by weight of the condensation product of toluenesulfonamide and formaldehyde per 100 parts of said resin, from about 0.1 to about 5 parts by weight of copper 8-quinolinolate per 100 parts of said resin and from about 0.1 to about 5 parts by weight of a compound selected from the group consisting of cadmium ricinoleate and calcium ricinoleate per 100 parts of said resin.

7. A composition as described in claim 6 wherein the vinyl chloride-containing resin is polyvinyl chloride. I

8. A composition as described in claim 6 wherein the vinyl chloride-containing resin is a copolymer of vinyl chloride and unsaturated materials copolymerizable therewith.

9. A composition as described in claim 6 wherein the vinyl chloride-containing resin is a copolymer of vinyl chloride and vinyl acetate.

10. A composition as described in claim 6 wherein the vinyl chloride-containin resin is a copolymer of vinyl chloride and diethyl maleate.

11. A process for preparing fungi and bacteria resistant vinyl halide-containing polymeric compositions which comprises incorporating into a vinyl halide-containing resin a plasticizer for said resin, the condensation product of toluenesulfonamide and formaldehyde, a minor amount of copper B-quinolinolate and a minor amount of a compound selected from the group consisting of cadmium ricinoleate and calcium ricinoleate.

12. A process for preparing fungi and bacteria resistant vinyl halide-containing polymeric compositions which comprises incorporating into a vinyl halide-containing resin a plasticizer for said resin, from about 1 to about 25 parts by weight of the condensation product of toluenesulfonamide and formaldehyde per 100 parts of said resin, from about 0.1 to about 10 parts by weight of copper B-quinolinolate per 100 parts of said resin and from about 0.1 to about 10 parts by weight of a compound selected from the group consisting of cadmium ricinoleate and calcium ricinoleate per 100 parts of said resin.

13. A process for preparing fungi and bacteria resistant vinyl halide-containing polymeric compositions which comprises incorporating into a vinyl halide-containing resin a plasticizer for said resin, from about 1 to about 5 parts by weight of the condensation product of toluenesulfonamide and formaldehyde per 100 parts of said resin, from about 0.1 to about 5 parts by weight of copper 8-quinolino1ate per 100 parts of said resin and from about 0.5 to about 5 parts by weight of a compound selected from the group consisting of cadmium ricinoleate and calcium ricinoleate per 100 parts of said resin.

14. A process for preparing fungi and bacteria resistant vinyl chloride-containing polymeric compositions which comprise incorporating into a vinyl chloride-containing resin a plasticizer for said resin, from about 1 to about 5 parts by weight of the condensation product of toluenesulfonamide and formaldehyde per 100 parts of said resin, from about 0.1 to about 5 parts by weight of copper 8-quino1ino1ate per 100 parts of REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,075,543 Reed et al Mar. 30, 1937 2,514,424 Kent July 11, 1950 2,567,910 Malone Jr Sept. 11, 1951 OTHER REFERENCES Lally et a1. (Modern Plastics), Dec. 1949, pp. 111, 112, 114, 116 and 156-162. 

1. FUNGI AND BACTERIA RESISTANT VINYL HALIDECONTAINING POLYMERIC COMPOSITIONS COMPRISING A VINYL HALIDE- CONDENSATION PRODUCT OF TOLUENESAID RESIN, THE CONDENSATION PRODUCT OF TOLUENESULFONAMIDE AND FORMALDEHYDE, A MINOR BUT EFFECTIVE AMOUNT OF COPPER 8-QUINOLINOLATE AND A COMPOUND SELECTED FROM THE GROUP CONSISTING OF CADMIUM RICINOLEATE AND CALCIUM RICINOLEATE, THE AMOUNT OF THE CONDENSATION PRODUCT OF TOLUENESULFONAMIDE AND FORMALDEHYDE BEING SUFFICIENT TO COMPATIBILIZE THE COPPER 8-QUINOLINOLATE IN THE RESIN COMPOSITION AND THE AMOUNT OF RICINOLEATE BEING A MINOR AMOUNT SUFFICIENT TO PREVENT CRYSTALLIZATION OR BLOOMING OF THE COPPER 8-QUINOLINOLATE FROM THE RESIN COMPOSITION UNDER CONDITIONS OF APPLICATION AND USE. 